Process of producing anilide compound

ABSTRACT

A process of producing an anilide compound, including reacting an acid fluoride with an N-silylaniline compound in the presence of a basic compound, is provided. According to the process, a desired anilide compound can be produced in a high yield without requiring a filtering step.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process of producing an anilidecompound.

2. Description of the Prior Art

To produce an anilide compound, conventionally, a method is knownwherein an acid fluoride and an aniline compound are reacted. However,in this reaction, since hydrogen fluoride is produced concomitantly, fora reason of safety, it is required to catch the hydrogen fluoride usingan acid scavenger, such as a tertiary amine and a basicnitrogen-containing compound. In addition, the use of a tertiary amineproduces an amine hydrofluoride in the form of a solid and a step isrequired to filter off this salt, which is a defect.

On the other hand, the reaction of an acid fluoride with anN-silylaniline compound proceeds hardly or even if they are reacted, theyield is very low.

SUMMARY OF THE INVENTION

Therefore, an object of the present invention is to provide a process ofproducing efficiently an anilide compound with the above problems beingsolved and without requiring a filtering step.

The inventors of the present invention have investigated intensively toattain the above object and have found that the above object can beattained by the following process.

The present invention provides a process of producing an anilidecompound, comprising reacting an acid fluoride with an N-silylanilinecompound in the presence of a basic compound.

According to the process of the present invention, an anilide compoundcan be synthesized in a high yield. This process does not require a stepof filtering an amine hydrogen fluoride in the form of a solid, whichstep is required in conventional processes. That is, since theby-product involved in the present process is a highly volatile silylfluoride, the by-product can be easily removed, for example, by vacuumdistillation.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is described in detail below.

Acid Fluoride

The acid fluoride used in the present invention includes, for example,compounds represented by the general formulas (1) to (2):

    R.sup.1 --CO--F                                            (1)

wherein R¹ denotes a substituted or unsubstituted monovalent organicgroup, and

    F--CO--R.sup.2 --CO--F                                     (2)

wherein R² denotes a substituted or unsubstituted bivalent organicgroup.

In the general formula (1), the substituted or unsubstituted monovalentorganic group denoted by R¹ includes, for example, an alkyl groupgenerally having 1 to 1,000 carbon atoms and preferably 1 to 500 carbonatoms, such as a methyl group, an ethyl group, and a propyl group; acycloalkyl group generally having 3 to 20 carbon atoms and preferably 3to 12 carbon atoms, such as a cyclopentyl group and a cyclohexyl group;an alkenyl group generally having 2 to 20 carbon atoms and preferably 2to 12 carbon atoms, such as a vinyl group and an ally group; an arylgroup generally having 6 to 30 carbon atoms and preferably 6 to 18carbon atoms, such as a phenyl group, a tolyl group, and a xylyl group;an aralkyl group generally having 7 to 30 carbon atoms and preferably 7to 19 carbon atoms, such as a benzyl group and a phenylethyl group;corresponding monovalent substituted groups in which part or all of thehydrogen atoms of the above monovalent groups have been replaced, forexample, with a halogen atom(s), such as chlorine, fluorine, andbromine, and/or a cyano group(s) (e.g., a chloromethyl group, achlorophenyl group, a perfluoroalkyl, a dibromophenyl group, or acyanoethyl group); and monovalent groups in the form of an oligomer orpolymer (e.g., monovalent perfluoropolyether groups, polyether groups,polyesther groups, polyimide groups and polyamide groups).

In the general formula (2), the substituted or unsubstituted bivalentorganic group denoted by R² includes, for example, an alkylene groupgenerally having 1 to 1000 and preferably 1 to 500 carbon atoms, such asa methylene group, an ethylene group, a propylene group, and atrimethylene group; a cycloalkylene group generally having 3 to 20 andpreferably 3 to 12 carbon atoms, such as a cyclopentylene group and acyclohexylene group; an alkenylene group generally having 2 to 20 carbonatoms and preferably 2 to 12 carbon atoms; an arylene group generallyhaving 6 to 30 carbon atoms and preferably 6 to 18 carbon atoms, such asa phenylene group, a tolylene group, a xylylene group, and a naphthylenegroup; corresponding bivalent substituted groups in which part or all ofthe hydrogen atoms of the above bivalent groups have been replaced, forexample, with a halogen atom(s), such as chlorine, fluorine, andbromine, and/or a cyano group(s) (e.g., a chloromethylene group, achlorophenylene group, and a perfluoroalkylene group); and bivalentgroups in the form of an oligomer or polymer (e.g., bivalentperfluoropolyether groups, polyether groups, polyesther groups,polyimide groups and polyamide groups).

Hereinbelow, specific examples of the acid fluoride are shown, wherein"a methyl group" is abbreviated to "Me" and "a phenyl group" isabbreviated to "Ph." ##STR1## wherein n is an integer of 0 to 300,

    F--(CF.sub.2 CF.sub.2 CF.sub.2 O).sub.n CF.sub.2 CF.sub.2 COF,

wherein n is an integer of 0 to 300, ##STR2## wherein m and n areindependently each an integer of 0 to 200, provided that m and n are notsimultaneously 0 and the average value of m+n ranges from 0 to 300, and##STR3## wherein l, m, and n are independently each an integer of 0 to100 and the average value of l+m+n ranges 0 to 50.

N-silylaniline Compound

In the present process, it is essential to use an N-silylanilinecompound as an aniline compound. The N-silylaniline compound includes,for example, a compound represented by the general formula (3): ##STR4##wherein a is an integer generally of 0 to 5 and preferably 0 to 2, R³,which are the same or different, each denote an alkyl group generallyhaving 1 to 10 carbon atoms and preferably 1 to 8 carbon atoms; analkenyl group generally having 2-8 carbon atoms and preferably 2-6carbon atoms, such as a vinyl group and an ally group; or an aryl groupgenerally having 6-10 carbon atoms and preferably 6-8 carbon atoms, suchas a phenyl group and a tolyl group, R⁴ denotes a hydrogen atom, analkyl group generally having 1 to 10 carbon atoms and preferably 1 to 8carbon atoms, or a group denoted by the formula: --Si(R³)₃ in which R³has the same meaning as defined above, R⁵ denotes a halogen atom, anitro group, or a group denoted by the formula: --Si(R³)₃ in which R³has the same meaning as defined above, and if a is 2 or more, R⁵ are thesame or different.

The group represented by R³ is preferably a methyl group because in thatcase the volatility of the silyl fluoride that is by-produced in thereaction in the present process, i.e., a compound denoted by thefollowing formula:

    F--Si(R.sup.3).sub.3

wherein R³ has the same meaning as defined above, becomes high.

Examples of the N-silylaniline compound denoted by the general formula(3) are shown below: ##STR5##

In the present process, the amount of the N-silylaniline compound issuch that the N-silyl group in the N-silylaniline compound is present inan amount of generally 1.0 to 1.5 mol and preferably 1.0 to 1.2 mol permol of the acid fluoride group (i.e., the --COF group).

Basic Compound

In the present process, by using a basic compound as a catalyst, theanilide compound can be obtained in a higher yield.

The basic compound includes, for example, a tertiary amine, such astriethylamine and tributylamine; and a basic nitrogen-containingcompound, such as 1,5-diazabicyclo 5.4.0!-7-undecene (DBU),pentamethylguanidine, and pyridine. Among them, a tertiary amine ispreferable and triethylamine is particularly preferable because in thatcase the yield of the obtained anilide compound is better.

The amount of the basic compound may be a so-called catalytic amount.

In the present process, use of a solvent is not particularly requiredbut optionally a fluorine-containing solvent, such as m-xylenehexafluoride, p-xylene fluoride, and benzotrifluoride, may be used.

Further, reaction temperature may be 0° to 100° C. and particularlypreferably 20° to 60° C. in view of reaction rate and because in thatcase the reaction temperature is higher than the boiling point of thetertiary amine which may be used as a catalyst. Reaction time isdetermined appropriately on the basis of the production scale and may begenerally 1 to 10 hours.

Reaction

The present process is carried out in accordance with the followingreaction: ##STR6## wherein R¹, R², R³, R⁴, R⁵, and a have the samemeanings as defined above.

In the present process, it is used that the bond energy between thesilicon atom of the N-silylaniline compound and the fluorine atom of theacid fluoride group is large.

After the reaction, the silyl fluoride, the catalyst, and the solventthat has been optionally added are removed easily by purification means,generally, such as vacuum distillation.

The present process is useful as a means of introducing a phenylamidegroup to the end of the molecular chain of a polymer, particularly, apolymer having perfluoroalkylene groups, bivalent perfluoropolyethergroups, or the like (i.e. cases in the above general formula (1), R¹ isa polymer chain and cases in the general formula (2), R² is a polymer).The obtained compound is useful as an intermediate for the production offluororubbers, fluorogels, fluorine-containing adhesives, and the like.

EXAMPLES

The present invention will now be described specifically by reference toExamples.

Example 1

10.0 g of an acid fluoride represented by the following formula:##STR7## 20.0 g of m-xylene hexafluoride, and 5.2 g (1.21 mol per mol ofthe acid fluoride group) of N-trimethylsilyl-N-methylmetachloroanilinewere charged in a 50-ml four-necked flask equipped with an agitatingrod, a thermometer, a Dimroth, and a dropping funnel and were stirred at23° C. for 1 hour. The reaction proceeded hardly, which was confirmed bygas chromatography. Then, when 0.5 g of triethylamine was added to themixture, heat was generated until the temperature reached 39° C. 1 hourafter the addition, the reaction conversion was 99.4%, which wasconfirmed by gas chromatography. The reaction mixture was subjected tovacuum distillation to obtain 10.8 g (yield: 86.8%) of a fraction havinga boiling point of 95° to 97° C./3 mmHg and a refractive index of 1.4864(25° C.). This fraction was subjected to ¹ H-NMR, IR, and elementaryanalysis. The results are shown below.

¹ H-NMR

δ 3.29 (s, N--CH₃, 3H)

δ 6.7-7.6 (m, arom., 4H)

IR

υ_(C)═O 1,700 cm¹

Elementary analysis

    ______________________________________    C            F        O        N      Cl    ______________________________________    Found   31.01%   52.12%   7.75%  2.26%  5.72%    Calculated            30.99%   52.18%   7.78%  2.29%  5.80%    ______________________________________

From the above results, it was confirmed that the obtained compound is acompound represented by the following formula: ##STR8##

Example 2

50.0 g of an acid fluoride represented by the following formula:##STR9## wherein m and n are independently each an integer of 1 to 30and the average value of m+n is 35, 5.2 g (1.2 mol per mol of the acidfluoride group) ofN-trimethylsilyl-N-methyl-m-(vinyldimethylsilyl)aniline, and 0.5 g oftriethylamine were charged into a 100-ml four-necked flask equipped withan agitating rod, a Dimroth, and a dropping funnel and were stirred at50° C. for 4 hours. After it was confirmed by gas chromatography thatthe peak intensity of theN-trimethylsilyl-N-methyl-m-(vinyldimethylsilyl)aniline was reduced toabout 20% of the initial value, the reaction mixture was subjected tovacuum distillation to remove volatile components to obtain a viscousliquid in an amount of 49.6 g (yield: 94%).

This viscous liquid had a viscosity of 1785 cSt (25° C.), a specificgravity of 1.807 (25° C.), and a refractive index of 1.3238 (25° C.).The results of ¹ H-NMR, IR, and elementary analysis confirmed that theliquid was a compound represented by the following formula: ##STR10##wherein m and n are independently each an integer of 1 to 30 and theaverage value of m+n is 35. The results of ¹ H-NMR, IR, and elementaryanalysis are shown below.

¹ H-NMR

δ 0.36 (s, Si--CH₃, 12H)

δ 3.35 (s, N--CH₃, 6H)

δ 5.7-6.4 (m, Si--CH═CH₂, 6H)

δ 7.1-7.6 (m, arom., 8H)

IR

υ_(C)═O 1,700 cm¹

Elementary analysis

    ______________________________________    Elementary analysis    C            F       O         N     Si    ______________________________________    Found  24.78%    64.24%  9.18%   0.43% 0.87%    Calculated           24.65%    64.33%  9.14%   0.45% 0.88%    ______________________________________

Example 3

1,000 g of an acid fluoride represented by the following formula:##STR11## wherein m and n are independently each an integer of 1 to 30and the average value of m+n is 35, 96.4 g (1.2 mol per mol of the acidfluoride group) ofN-vinyldiemthylsilyl-N-methyl-m-(vinyldimethylsilyl)aniline, and 10.0 gof triethylamine were charged into a 2-litter four-necked flask equippedwith an agitating rod, a Dimroth, and a dropping funnel and were stirredat 25° C. for 3 hours. After it was confirmed by gas chromatography thatthe peak intensity of theN-vinyldiemthylsilyl-N-methyl-m-(vinyldimethylsilyl)aniline was reducedto about 20% of the initial value, the reaction mixture was subjected tovacuum distillation to remove volatile components to obtain a viscousliquid in an amount of 956 g (yield: 94%).

This viscous liquid had a viscosity of 1849 cSt (25° C.), a specificgravity of 1.804 (25° C.), and a refractive index of 1.3249 (25° C.).The results of ¹ H-NMR, IR, and elementary analysis confirmed that theliquid was a compound represented by the following formula: ##STR12##wherein m and n are independently each an integer of 1 to 30 and theaverage value of m+n is 35. The results of ¹ H-NMR, IR, and elementaryanalysis are shown below.

¹ H-NMR

δ 0.37 (s, Si--CH₃, 6H)

δ 3.34 (s, N--CH₃, 3H)

δ 5.7-6.4 (m, Si--CH═CH₂, 3H)

δ 7.1-7.6 (m, arom., 4H)

IR

υ_(C)═O 1,700 cm¹

Elementary analysis

    ______________________________________    Elementary analysis    C            F       O         N     Si    ______________________________________    Found  24.69%    64.35%  9.22%   0.43% 0.86%    Calculated           24.65%    64.33%  9.14%   0.45% 0.88%    ______________________________________

What is claimed is:
 1. A process of producing an anilide compound,comprising reacting an acid fluoride with an N-silylaniline compound inthe presence of a basic compound.
 2. The process of producing an anilidecompound of claim 1, wherein said basic compound is a tertiary amine. 3.The process of claim 1, wherein said acid fluoride is a compoundrepresented by the general formula (1):

    R.sup.1 --CO--F                                            (1)

wherein R¹ denotes a substituted or unsubstituted monovalent organicgroup.
 4. The process of claim 3, wherein the substituted orunsubstituted monovalent organic group denoted by R¹ is a group selectedfrom the group consisting of an alkyl group having 1 to 1,000 carbonatoms; a cycloalkyl group having 3 to 20 carbon atoms; an alkenyl grouphaving 2 to 20 carbon atoms; an aryl group having 6 to 30 carbon atoms;an aralkyl group having 7 to 30 carbon atoms; corresponding monovalentsubstituted groups in which part or all of the hydrogen atoms of theabove monovalent groups have been replaced with a halogen atom(s) or acyano group(s); and monovalent groups in the form of an oligomer orpolymer.
 5. The process of claim 1, wherein said acid fluoride is acompound represented by the general formula (2):

    F--CO--R.sup.2 --CO--F                                     (2)

wherein R² denotes a substituted or unsubstituted bivalent organicgroup.
 6. The process of claim 5, wherein the substituted orunsubstituted bivalent organic group denoted by R² is a group selectedfrom the group consisting of a substituted or unsubstituted alkylenegroup having 1 to 1,000 carbon atoms; a substituted or unsubstitutedcycloalkylene group having 3 to 20; a substituted or unsubstitutedalkenylene group having 2 to 20 carbon atoms; a substituted orunsubstituted arylene group having 6 to 30 carbon atoms; and bivalentgroups in the form of an oligomer or polymer.
 7. The process of claim 1,wherein said acid fluoride is selected from the group consisting of##STR13## wherein n is an integer of 0 to 300,

    F--(CF.sub.2 CF.sub.2 CF.sub.2 O).sub.n CF.sub.2 CF.sub.2 COF,

wherein n is an integer of 0 to 300, ##STR14## wherein m and n areindependently an integer of 0 to 200, provided that m and n are notsimultaneously 0 and the average value of m+n ranges from 0 to 300, and##STR15## wherein l, m, and n are independently an integer of 0 to 100and the average value of l+m+n ranges 0 to
 50. 8. The process of claim1, wherein said N-silylaniline compound is a compound represented by thegeneral formula (3): ##STR16## wherein a is an integer of 0 to 5, R³,which are the same or different, and each denote an alkyl group having 1to 10 carbon atoms; an alkenyl group having 2 to 8 carbon atoms; or anaryl group having 6 to 10 carbon atoms, R⁴ denotes a hydrogen atom, analkyl group having 1 to 10 carbon atoms, or a group denoted by theformula: --Si(R³)₃ in which R³ has the same meaning as defined above, R⁵denotes a halogen atom, a nitro group, or a group denoted by theformula: --Si(R³)₃ in which R³ has the same meaning as defined above,and if a is 2 or more, R⁵ are the same or different.
 9. The process ofclaim 8, wherein the compound represented by the above general formula(3) is selected from the group consisting of ##STR17##
 10. The processof claim 1, wherein said basic compound is selected from the groupconsisting of tertiary amines, such as triethylamine and tributylamine,1,5-diazabicyclo 5.4.0!-7-undecene (DBU), pentamethylguanidine, andpyridine.
 11. The process of claim 10,. wherein said basic compound istriethylamine.
 12. The process of claim 1, wherein the amount of theN-silylaniline compound is such that the N-silyl group of theN-silylaniline compound is present in an amount of 1.0 to 1.5 mol andpreferably 1.0 to 1.2 mol per mol of the --COF group possessed by theacid fluoride compound.